EP0647183B1 - Lamellenartig polymerer körper und verfahren zu seiner herstellung - Google Patents

Lamellenartig polymerer körper und verfahren zu seiner herstellung Download PDF

Info

Publication number
EP0647183B1
EP0647183B1 EP92904514A EP92904514A EP0647183B1 EP 0647183 B1 EP0647183 B1 EP 0647183B1 EP 92904514 A EP92904514 A EP 92904514A EP 92904514 A EP92904514 A EP 92904514A EP 0647183 B1 EP0647183 B1 EP 0647183B1
Authority
EP
European Patent Office
Prior art keywords
polymeric
layers
polymeric material
lamellar
matrix
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92904514A
Other languages
English (en)
French (fr)
Other versions
EP0647183A1 (de
EP0647183A4 (de
Inventor
Walter J. Schrenk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0647183A4 publication Critical patent/EP0647183A4/de
Publication of EP0647183A1 publication Critical patent/EP0647183A1/de
Application granted granted Critical
Publication of EP0647183B1 publication Critical patent/EP0647183B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/18Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/30Extrusion nozzles or dies
    • B29C48/304Extrusion nozzles or dies specially adapted for bringing together components, e.g. melts within the die
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • B29C70/585Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres incorporation of light reflecting filler, e.g. lamellae to obtain pearlescent effet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00Producing optical elements, e.g. lenses or prisms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/18Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side
    • B32B3/22Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side of spaced pieces
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/28Interference filters
    • G02B5/285Interference filters comprising deposited thin solid films
    • G02B5/287Interference filters comprising deposited thin solid films comprising at least one layer of organic material
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3008Polarising elements comprising dielectric particles, e.g. birefringent crystals embedded in a matrix
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0031Refractive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/42Alternating layers, e.g. ABAB(C), AABBAABB(C)
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/416Reflective
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/913Material designed to be responsive to temperature, light, moisture

Definitions

  • the present invention relates to a multilayered polymeric body of optically thick, thin, and/or very thin plate-like or ribbon-like layers of one or more polymers within a matrix of another polymer, which body reflects light and can be fabricated to have a silvery or hued (eg gold or copper) metallic appearance, or a nonconventional hued (eg blue or green) appearance, or even an iridescent appearance, and to methods of producing such a polymeric body.
  • a silvery or hued eg gold or copper
  • a nonconventional hued eg blue or green
  • such metal coated plastic articles are formed by electroplating or by the vacuum, vapor, or chemical deposition of a thin metal layer on the surface of the article.
  • Such coatings are subject to the chipping and flaking of the metal coatings as well as corrosion of the metal over time. If additional protective layers must be applied over the metal coating to protect it, additional labor and materials costs are involved. Further, there may be environmental disposal problems with some metal deposition processes.
  • multilayer articles of polymers are known, as are methods and apparatuses for making such articles.
  • multilayered articles may be prepared utilizing multilayer coextrusion devices as described in commonly-assigned US-A-3,773,882 and US-A-3,884,606 to Schrenk.
  • Such devices are capable of simultaneously extruding diverse thermoplastic polymeric materials in continuous layers having substantially uniform layer thicknesses.
  • the number of layers may be multiplied by the use of a device as described in commonly-assigned US-A-3,758,647 to Schrenk et al.
  • Schrenk et al., US-A-3,576,707 discloses multilayered iridescent plastic articles formed of at least 10 layers of resinous materials, wherein contiguous adjacent layers are of diverse resinous material and at least 20 percent of the layers have a thickness of 0.05 to 5 micrometers.
  • Im et al. US-A-4,540,623, teaches a multilayer laminated article which includes a polycarbonate as one of the alternating continuous layers.
  • the articles of Im are intended to be transparent rather than reflective and to exhibit optical properties comparable to a pure polycarbonate polymer.
  • Alfrey, Jr. et al US-A-3,711,176, teaches a multilayered highly reflective thermoplastic body fabricated using thin film techniques. That is, the reflective thin film layers of Alfrey, Jr. et al relied on the constructive interference of light to produce reflected visible, ultraviolet, or infrared portions of the electromagnetic spectrum. Such reflective thin films have found use in decorative items because of the iridescent reflective qualities of the film.
  • the films of Alfrey, Jr. et al are extremely sensitive to thickness changes, and it is characteristic of such films to exhibit streaks and spots of nonuniform color. Further, color reflected by such films is dependent on the angle of incidence of light impinging on the film. Thus, such films are not practical for uses which require uniformity of reflectivity. Moreover, such films are not practical to thermoform into articles where uniformity of light reflectance is needed as localized thinning of the layers during thermoforming causes alterations in the reflective characteristics of the films.
  • both the Alfrey, Jr. et al films and the multilayer films and articles made up of substantially continuous layers have some limiting characteristics inherent in their construction.
  • the continuous layers must adhere to themselves to hold the film together. This may necessitate the use of intervening adhesive layers which could adversely affect the optical properties of the film and certainly add to the overall thickness of the film. Further, no gas or other fluid can be permitted at the interface between any of the layers as this may contribute to the delamination of the layers.
  • each of the materials used in the layers exerts an effect on the overall mechanical properties of the film. For example, if one of the polymers used is brittle, the layers of brittle material will have an effect on the overall properties of the multilayer film.
  • a polymeric reflective film, sheet or body which can be fabricated into a variety of parts and which can exhibit a uniform reflective appearance or a silvery iridescent appearance over a range of processing conditions and part geometry.
  • a polymeric reflective film or body which will hold together even if some or all of the individual layers do not, there is a need for a body in which gas or other fluid can be present at layer interfaces without adversely affecting the optical and mechanical properties of the body, and there is a need for a multilayer reflective body which has mechanical properties which are substantially independent of the mechanical properties of at least some of the layers in the body.
  • the present invention meets those needs by providing a lamellar reflective polymeric body containing no metals, and a method of making that body which polymeric body can be fabricated and/or post-formed into a variety of parts.
  • fabrication and/or post-forming can be accomplished without alteration of its uniform reflective appearance.
  • the body comprises discontinuous layers of at least one polymeric material within a matrix of another polymeric material which polymers differ in refractive index.
  • the layers of the polymeric material may be either optically thick, optically thin (that is, iridescent interference layers) or optically very thin.
  • the optically thick layers are too thick to cause visible iridescent effects (visually perceived as a variety of colors), while the very thin layers are too thin to cause such effects.
  • the resulting multilayered lamellar polymeric body depending upon the layer thicknesses selected, may reflect substantially white light and exhibit a silvery, metallic appearance, or may have bands of iridescent color.
  • the discontinuous multilayer construction provides a number of advantageous mechanical properties.
  • Such properties include high tensile properties in one direction but lower in a direction transverse to the discontinuous ribbon-like layers, the ability to tailor flexibility and ductility into the body, and the ability to include overlapping gas barrier layers into the multilayer construction.
  • reflectance refers to total reflectance (that is, ratio of reflected wave energy to incident wave energy) sufficiently specular in nature such that the polymeric body has a metallic appearance.
  • reflectance measurement refers to reflectance of light rays into an emergent cone with a vertex angle of 15 degrees centered around the specular angle.
  • a specific intensity of reflectance when used herein, is the intensity of reflection which occurs at a wavelength where negligible absorption of light occurs.
  • a silver appearing article reflects substantially all visible wavelengths, whereas the introduction of a dye to achieve other metallic hues will necessarily lower reflectivity of the body at the absorbing wavelengths. Wavelengths unaffected by the dye will be reflected at essentially the same intensity as a non-dyed sample, and it is at these unaffected wavelengths to which the intensity of reflection is referring.
  • the reflectance referred to is the peak reflectance observed.
  • a lamellar reflective polymeric body of at least first and second diverse polymeric materials is provided, the body having at least first and second major surfaces.
  • the body includes a plurality of discontinuous layers of the first polymeric material within a matrix of the second polymeric material, with layers of the first polymeric material having their major interfaces aligned substantially parallel to the major surfaces of the body.
  • the number of layers of the first polymeric material in the body is preferably sufficient such that at least 30 percent of light incident on the body is reflected.
  • the individual layers of the first polymeric material in the body and those portions of the second polymeric material sandwiched between the individual layers of the first polymeric material have an optical thickness of not more than 0.09 micrometers (that is, are optically very thin), between 0.09 micrometers and 0.45 micrometers (that is, are optically thin), or not less than 0.45 micrometers (that is, are optically thick).
  • At least 75 percent of the individual layers of first polymeric material and those portions of second polymeric material sandwiched between the individual layers of first polymeric material have an optical thickness of 0.45 micrometers or greater or 0.09 micrometers or less to produce a uniformly reflective, metallic appearing body.
  • the individual layers of first polymeric material and portions of second polymeric material sandwiched therebetween should have an optical thickness such that no visibly perceived iridescence is reflected from the body.
  • a portion or all of the individual layers of first polymeric material and second polymeric material sandwiched therebetween have optical thicknesses in the range of from 0.09 micrometers to 0.45 micrometers to produce a body which has a colored and/or silvery iridescent appearance.
  • the first and second polymeric materials differ from each other in refractive index by at least 0.03.
  • a fluid such as air may be present at a plurality of the major interfaces of the first and second polymeric materials.
  • the body may comprise from less than one hundred to several thousand layers of the first polymeric material with alternating portions of the second polymeric material therebetween.
  • Increasing the number of layers in the polymeric body has been found to increase its reflectivity (that is, the percentage of incident light reflected from the body).
  • the degree of reflectivity of the article may be controlled.
  • the reflective body of the present invention may be made up of two or more generally transparent polymer resins.
  • the polymers used in the practice of the present invention may be rigid or elastomeric, or have varying degrees of flexibility.
  • Preferred are thermoplastic resins which are capable of being post formed into a variety of shapes.
  • the first polymeric material may be polymethyl methacrylate and the second polymeric material may be polystyrene.
  • the first polymeric material may be a gas barrier material.
  • gas barrier material such as copolymers of ethylene and vinyl alcohol, polyvinylidene chloride, nitrile polymers, and nylons may be used in the multilayer body.
  • the layers of the first polymeric material may be present in the form of elongate, flat, ribbon-like layers which are substantially continuous in a first plane parallel to one of the major surfaces of the body and discontinuous in a second plane transverse to the first plane.
  • the layers of the first polymeric material may be present in the form of platelet-like layers which are substantially discontinuous along planes generally parallel and transverse to one of the major surfaces of the body.
  • coloring agents such as dyes or pigments into one or more of the individual interior layers of the polymeric body or into the continuous polymeric matrix of the body.
  • the coloring agents may be selected to give the polymeric body a metallic appearance other than its normal silvery appearance such as bronze, copper, or gold, for example.
  • pigmented coloring agents may be used in combination to provide desirable coloring and optical properties.
  • a pigmented white coloring agent may be used in an interior layer while a colored dye, such as blue, yellow, red, or green may be included in the continuous polymeric matrix to provide a unique reflective colored effect.
  • the surface of the body is smooth to give a highly reflective appearance
  • a solvent may be used to etch the surface of the multilayer body to provide a matte or pewter look to the body.
  • the body may be embossed with a variety of patterns to provide desirable optical effects.
  • the interior layers of the reflective body may include layers of two or more different polymers in a matrix of a third polymer.
  • a lamellar reflective polymeric body of at least first and second diverse polymeric materials is provided, the body having at least first and second major surfaces.
  • the body comprises a plurality of individual layers within a matrix of a third polymeric material, with each individual layer comprising at least three or more alternating layers of the first and second polymeric materials within the matrix.
  • the alternating layers of the first and second polymeric materials have their major interfaces aligned substantially parallel to the major surfaces of the body, with the number of alternating layers of the first and second polymeric materials being sufficient such that at least 30 percent of light incident on the body is reflected.
  • the individual layers of the first and second polymeric materials have optical thicknesses of not more than 0.09 micrometers (that is, are optically very thin), between 0.09 micrometers and 0.45 micrometers (that is, are optically thin), or not less than 0.45 micrometers (that is, are optically thick).
  • the first and second polymeric materials differ from each other in refractive index by at least about 0.03.
  • At least 75 percent of the individual layers of the first and second polymeric materials have an optical thickness of at least 0.45 micrometers to produce a uniformly reflective, metallic- appearing body.
  • a portion or all of the individual layers of first polymeric material and second polymeric material sandwiched therebetween have optical thicknesses in the range of from 0.09 micrometers to 0.45 micrometers to produce a body which has a colored and/or silvery iridescent appearance.
  • the polymers making up the various layers of the body may be chosen to give the body specific mechanical or optical properties.
  • the third polymeric material which makes up the continuous matrix may be elastomeric to produce a flexible reflective body.
  • Polymers may be selected to provide a reflective body which is post formable and/or thermoformable.
  • coloring agents such as pigments or dyes may be incorporated into one or more of the polymeric materials as previously described. Reflectivity of the body may be controlled by controlling the number of layers of polymers in the body.
  • the body comprises from less than one hundred to several thousand layers of the first and second polymeric materials.
  • the layers of the first and second polymeric materials are substantially continuous in a first plane parallel to one of the major surfaces of the body and discontinuous in a second plane transverse to the first plane to form elongate ribbon-like elements.
  • the layers of the first and second polymeric materials are substantially discontinuous along planes parallel and transverse to one of the major surfaces of the body to form platelet-like elements.
  • the reflective polymeric body of the present invention may also be fabricated to act as a birefringent light polarizer which polarizes a broad band of the electromagnetic spectrum.
  • the polarizer is fabricated of at least first and second diverse polymeric materials, with the body having at least first and second major surfaces.
  • the body includes a plurality of layers of the first polymeric material within a matrix of the second polymeric material, with the layers of the first polymeric material having their major interfaces aligned substantially parallel to the major surfaces of the body.
  • the number of layers of the first polymeric material is sufficient such that at least 30 percent of light incident on the polarizer is reflected in the plane of polarization.
  • the individual layers of the first polymeric material and those portions of the second polymeric material sandwiched between individual layers of the first polymeric material have an optical thickness of not more than 0.09 micrometers or at least 0.45 micrometers, with the first and second polymeric materials differing from each other in refractive index by at least 0.03 in one plane of the polarizer.
  • the difference in refractive index between the first and second polymeric materials is caused by selecting polymers having differing stress optical coefficients and then stretching those materials in a uniaxial direction to orient the polymeric materials.
  • the unique arrangement of layers of diverse polymeric materials may also provide a useful body even where reflective properties are not required.
  • the arrangement of discontinuous layers of one polymer in a continuous matrix of another polymer permits the fabrication of bodies which have physical properties which are controllable and substantially independent of the materials used for the discontinuous layer. Additionally, because of the continuous matrix of the second polymer surrounding the layers, delamination of the first and second polymers at their respective interfaces does not adversely affect the overall body; catastrophic delamination of the body does not occur.
  • a lamellar polymeric body of at least first and second diverse polymeric materials is provided, with the body having at least first and second major surfaces.
  • the body includes a plurality of layers of the first polymeric material within a matrix of the second polymeric material. Further, the layers of the first polymeric material are substantially discontinuous along planes parallel and/or transverse to one of the major surfaces of the body to form platelet-like elements.
  • the polymeric body may be fabricated so that the first polymeric material is rubbery (or elastomeric) and the second polymeric material is brittle. This results in a polymeric body which has greater flexibility than one fabricated of the second polymeric material alone.
  • both polymeric materials may be elastomers. If the matrix polymer is elastomeric and the first polymeric material is not, the body still possesses elastomeric properties. Where the first polymer is in the form of discontinuous platelet-like elements, the body retains elastomeric properties in all directions.
  • the bodies of the present invention can be prepared by a method comprising the steps of providing a first stream of a first heat plastified polymeric material and a second stream of a second heat plastified polymeric material, and encapsulating discrete portions of the first polymeric material in the second polymeric material by coextruding the polymeric materials to form a plurality of discontinuous ribbon-like layers of the first polymeric material within a matrix of the second polymeric material to form the reflective polymeric body.
  • the discontinuous layers of the first polymeric material are arranged to have their major interfaces aligned substantially parallel to the major surfaces of the body such that at least 30 percent of light incident on the body is reflected.
  • the individual layers of the first polymeric material in the body, and those portions of the second polymeric material sandwiched between the individual layers of the first polymeric material, have an optical thickness of not more than 0.09 micrometers, between 0.09 micrometers and 0.45 micrometers, or not less than 0.45 micrometers, and the first and second polymeric materials differ from each other in refractive index by at least 0.03.
  • the ribbon-like layers may be further divided into a series of platelet-like layers to produce layers which are discontinuous in all major planar dimensions. This step of dividing the ribbon-like layers into platelet-like layers may be accomplished, for example, by passing the ribbon-like layers through a reciprocating feed plate or valve.
  • a method for the production of a lamellar reflective polymeric body comprising the steps of providing a first stream of a first heat plastified polymeric material and a second stream of a second heat plastified polymeric material.
  • the polymeric materials are coextruded to form alternating layers of the first and second polymeric materials, and then individual ones of the alternating layers of the first and second polymeric materials are encapsulated in a third polymeric material to form a plurality of discontinuous ribbon-like elements of the alternating layers of the first and second polymeric materials within a matrix of the third polymeric material to form the reflective polymeric body.
  • the alternating layers of the first and second polymeric materials have their major interfaces aligned substantially parallel to the major surfaces of the body such that at least 30 percent of light incident on the body is reflected, with the individual layers of the first and second polymeric materials having optical thicknesses of not more than 0.09 micrometers, or between 0.09 micrometers and 0.45 micrometers, or not less than 0.45 micrometers.
  • the first and second polymeric materials differ from each other in refractive index by at least 0.03.
  • the ribbon-like elements may be further divided into a series of platelet-like elements to produce elements which are discontinuous in all major planar dimensions. This may be accomplished by dividing the ribbon-like elements into platelet-like elements is by passing the ribbon-like elements through a reciprocating feed plate or valve.
  • a method for the production of a lamellar reflective polymeric body including the steps of, providing a first stream of a first heat plastified polymeric material and a second stream of a second heat plastified polymeric material. Alternating slugs of the first and second polymeric materials are then fed to a flow passage where the slugs are formed into discontinuous alternating layers of the first and second polymeric materials due to the viscosities of the polymers flowing through the passage.
  • first and second polymeric materials are then encapsulated in a third polymeric material to form a plurality of discontinuous ribbon-like elements of the alternating layers of first and second polymeric materials within a matrix of the third polymeric material to form the reflective polymeric body.
  • the alternating layers of the first and second polymeric materials have their major interfaces aligned substantially parallel to the major surfaces of the body such that at least 30 percent of light incident on the body is reflected, with the individual layers of the first and second polymeric materials having optical thicknesses of not more than 0.09 micrometers, between 0.09 micrometers and 0.45 micrometers, or not less than 0.45 micrometers.
  • the first and second polymeric materials differ from each other in refractive index by at least 0.03.
  • the feeding alternating slugs of the first and second polymeric materials to a flow passage is accomplished by passing the first and second polymeric materials through a reciprocating valve.
  • the frequency of reciprocation of the valve is controlled to control the size of the alternating layers.
  • the present invention provides a highly reflective lamellar multilayer polymeric body made up of from less than a hundred to several thousand layers of at least one polymer within a matrix of another polymer, which polymers differ from each other in refractive index.
  • the individual layers of the polymeric material have an optical thickness of not more than 0.09 micrometers, between 0.09 micrometers and 0.45 micrometers, or not less than 0.45 micrometers, where the optical thickness is defined as the product of the individual layer thickness times the refractive index of the polymeric material which makes up that layer.
  • the lamellar multilayer reflective polymeric body of the present invention is made up of multiple optically thick and/or optically thin and/or optically very thin layers.
  • an optically thin film can be described as a film thinner than one wavelength of light at which the film will be applied.
  • a thin film is described in the literature as one whose thickness, D, is less than 0.5 micrometer or whose optical thickness, ND (where N is the refractive index of the material) is less than 0.7 micrometers.
  • first order visible reflections of violet (0.38 micrometer wavelength) to red (0.68 micrometer wavelength) can be obtained with layer optical thicknesses between 0.075 - 0.25 micrometers.
  • Iridescent films may also be designed to reflect visible light at higher order reflectances, although at lower intensities.
  • such thin film polymeric bodies are strongly dependent upon film (and individual layer) thickness to determine reflected wavelength.
  • the body will exhibit colored or silvery iridescence.
  • the multilayer bodies are designed so that they do not display the vivid iridescence which is displayed when using optically thin layers.
  • the use of layers too thick or too thin to cause iridescence, alone or in combination with each other result in a reflection which is essentially silver and non-iridescent. This silvery appearance is due to higher order reflections from the thick and/or very thin layers being so closely spaced that the human eye perceives the reflection to be essentially non-iridescent.
  • n refractive index of the polymer
  • d physical thickness of the layer in micrometers.
  • Articles made in accordance with this embodiment of the invention exhibit a uniform silvery reflective appearance.
  • the reflected wavelength of light from this embodiment of the multilayer polymeric body of the present invention is independent of both individual layer and total structure thickness over a wide processing range. Uniformity of reflection is inherent in the design of the body. Moreover, a gradient of layer thicknesses through the thickness of the body is neither detrimental nor advantageous to the appearance of the body as long as a substantial majority of the individual layers of the polymers maintains an optical thickness equal to or greater than 0.45 micrometers or equal to or less than 0.09 micrometers. This again contrasts with the optically thin film embodiment of the invention which reflects broad or narrow bandwidths depending upon layer thickness gradient.
  • the preferred coextrusion process for fabricating the polymeric bodies of the present invention may introduce layer thickness variations both through the thickness of the body and in the plane of individual layers. Variation in layer thicknesses of each polymeric component can be as much as 300 percent or more. However, useful reflective bodies and articles may be made even with such wide variations as long as a substantial majority of the layers have an optical thickness of not more than 0.09 micrometers or not less than 0.45 micrometers. With this condition met, there is an absence of visibly perceived interference colors reflected from bodies and articles of this embodiment of the present invention.
  • the absence of the iridescent interference colors is somewhat subjective to the human eye. However, we have found that about 75 percent of the layers in the body should have optical thicknesses greater than 0.45 micrometers or less than 0.09 micrometers to obtain the broad band, visually uniform reflectance of substantially all wavelengths (white light) which characterizes this embodiment of the present invention. A minority of 25 percent or fewer of the layers having optical thicknesses in the range of 0.1 to 0.45 micrometers have been found to have interference reflections of a sufficiently low intensity so that the body will have essentially no visibly perceived iridescence.
  • the reflective polymeric bodies of the present invention become more highly reflective of incident light (that is, transmit less light) as the number of layers is increased.
  • the number of layers is sufficient to produce an article which will reflect at least 30 percent of the incident light, for those wavelengths for which there is negligible absorption. Reflectances below 30 percent are not sufficient to be readily observed. If it is desired to use the reflective polymeric body of the present invention as a mirror, adding additional layers will increase the reflectance of the body to 50 percent or higher to produce a silvery, mirror-like appearance.
  • the reflectivity of the bodies is also dependent upon the difference in refractive index between the two polymers used. That is, the greater the difference in refractive index, the greater the reflectivity of the body. Accordingly, it can be seen that the reflective nature of the polymeric bodies may be controlled by the selection of polymers having differing refractive indices and by fabricating the body to have additional layers.
  • the reflective multilayered polymeric bodies of the present invention may comprise alternating layers of a wide variety of generally transparent thermoplastic materials.
  • Copolymers of the above resins are also useful such as hydrolyzed ethylene vinyl acetate, styrene and hydroxy ethylacrylate, styrene and maleic anhydride, styrene-butadiene block copolymers, styrene and methyl methacrylate, and styrene and acrylic acid.
  • Other useful polymeric materials include polyetheretherketones, polybutene, maleic anhydride grafted polyolefins such as Admer (available from Mitsui Chemicals) and Plexar (available from Quantum Chemicals), and copolymers of ethylene and vinyl acetate such as CXA (available from du Pont). The latter three polymers are particularly useful as adhesive layers to bond other polymeric layers together in the multilayer construction.
  • a condition for the selection of the polymers to make up the layers and matrix of the body is that the polymers selected have refractive indices which differ from each other by at least 0.03. Further, the polymers should be compatible in processing temperatures so that they may be readily coextruded.
  • Multilayer bodies in accordance with the present invention are most advantageously prepared by employing principles similar to those described in US-A-3,565,985, US-A-3,759,647, US-A-3,773,882, and US-A-3,884,606, with respect to multilayer coextrusion.
  • Such devices are capable of providing substantially continuous multilayered, simultaneously extruded thermoplastic materials having controllable layer thicknesses.
  • FIG. 1 An apparatus for preparing lamellar polymeric bodies of the present invention is illustrated in Fig. 1.
  • Apparatus 10 includes, in cooperative combination, first, second, and optional third sources of heat plastified polymeric resins for extruders 11, 12, and 13, respectively.
  • Optional third source of polymer resin is used when it is desired that the first and second polymers adhere to each other in the final polymeric body.
  • a "glue" layer of a third polymer may be interposed between the first and second polymers as explained in further detail below.
  • Extruders 11, 12, and 13 discharge the heat plastified polymeric resins into conduits 14, 15, and 16, respectively.
  • a coextrusion feedblock die 17 is in operative combination with conduits 14, 15, and 16 and receives first, second, and optional third heat plastified streams therefrom.
  • Die 17 defines an extrusion orifice 18 from which issues a composite stream of polymeric material having ribbon-like layers of a first polymeric material embedded within a matrix of a second polymeric material.
  • the first and second polymers may be adhered together by a "glue" layer of a third polymer.
  • the composite stream passes optionally through a mechanical manipulating section 20 which serves to rearrange the original ribbon layers in a matrix composite stream into a stream having more than the original number of ribbon layers as taught in the aforementioned US-A-3,565,985 and US-A-3,759,647. Additional manipulating sections may be arranged in series to further multiply the number of layers in the stream.
  • the number of additional ribbon layers created using the manipulation devices of the aforementioned patents is determined by the number of ribbon layers divided by the layer-dividing vane in those devices. Ribbon layers not cut by the dividing vane are not multiplied. This is in contrast to a substantially continuous multilayer construction in which all layers are cut by the dividing vane.
  • the interfacial area of each ribbon is increased in the lateral spreading region of the mechanical manipulating devices. For each layer multiplication stage, the width of the ribbon layers is doubled and the thickness is halved, for polymers having reasonably matched viscosities. Where the ribbon layers have a higher viscosity than the matrix polymer, there will be a correspondingly lesser change in the shape of the ribbon layers after manipulation.
  • the multilayered stream is then passed into a shaping die 22 which is so constructed and arranged that streamlined flow is maintained therein.
  • a shaping die 22 which is so constructed and arranged that streamlined flow is maintained therein.
  • Such an extrusion die is described in US-A-3,557,265. While a sheet or film forming die 22 is illustrated, it will be appreciated by those skilled in the art that a forming die of any desired configuration may be use to extrude not only films and sheets, but also other profiles and shapes.
  • the configuration of the shaping die can vary and can be such as to reduce the thickness of each of the ribbon-like layers.
  • the precise degree of reduction in thickness of the ribbon-like layers delivered from the mechanical orienting section, the configuration of the die, and the amount of mechanical working of the body after extrusion are all factors which affect the thickness of the Individual layers in the final body.
  • Fig. 2 depicts schematically a sectional view of die 17 suitable for the production of the polymeric body of the present invention.
  • Die 17 comprises a die body 30 defining a first inlet plenum 32 in operative communication with a first polymer source through conduit 14.
  • Die body 30 also defines a second or intermediate polymer plenum 34 in operative communication with a second polymer source through conduit 15.
  • An optional third plenum 36 is defined by die body 30 and is in operative communication with an optional source of polymer through conduit 16.
  • the adhesive polymer is supplied to second plenum 34, while the second polymer is supplied from conduit 16 to optional third plenum 36.
  • discharge plenum 38 terminates in discharge orifice passage 18.
  • a first dividing means 40 is disposed between inlet plenum 32 and second plenum 34.
  • a second dividing means 42 is disposed between second plenum 34 and third plenum 36.
  • An optional third dividing means 44 is disposed between third plenum 36 and discharge plenum 38.
  • First dividing means 40 has a plurality of passages 46 which provide communication between inlet plenum 32 and a location within second dividing means 42.
  • the passages 46 may be round, square, or rectangular in cross section and arranged in either rows or staggered arrays.
  • Second dividing means 42 has a plurality of passages 48 which provide communication between second plenum 34 and a location within optional third dividing means 44. Again, the passages may be round, square, or rectangular in cross section, and may be arranged in either rows or staggered arrays.
  • Optional third dividing means 44 also has a plurality of passages 50 which provide communication between third plenum 36 and discharge plenum 38.
  • a first heat plastified polymeric resin is supplied through conduit 14 into inlet plenum 32. From plenum 32, the polymeric material flows through passages 46 and is discharged within passages 48. A second heat plastified polymeric resin is supplied through conduit 15 into intermediate plenum 34. The second polymer flows through passages 48 around the discharge points of the first polymeric material and encapsulates the ribbons of the first polymer in a continuous matrix.
  • the adhesive polymer is supplied through conduit 15 into intermediate plenum 34, and the second heat plastified polymer is supplied through conduit 16 into third plenum 36.
  • the second polymer flows around and encapsulates ribbons of the first polymer, now coated with a layer of an adhesive polymer, and encapsulates the two in a continuous matrix.
  • a composite stream made up of multiple ribbon-like layers of a first polymer in a continuous matrix of a second polymer is formed and discharges through orifice 18.
  • the composite polymer stream is discharged through shaping die 22 to form a polymeric body 60 as illustrated in Fig. 3.
  • the polymeric body 60 includes a plurality of layers of a first polymeric material in the form of substantially continuous ribbons 62 embedded in a matrix 64 of a second polymer.
  • the ribbons are substantially continuous in a first plane parallel to a major horizontal surface of the body and are discontinuous in a plane transverse thereto.
  • the cross sectional shape and dimensions of the ribbons 62 are determined by the relative flow rates, the flow patterns within the manipulating section, and the shaping die as well as the viscosity and elasticity of the polymers and their interfacial tension.
  • a reflective multilayered polymeric body which reflects at least 30 percent of the light incident thereon.
  • the thicknesses of the layers of first polymeric material and those portions of the second polymeric material sandwiched between layers of the first polymeric material are controlled so that the individual layers of first polymeric material and portions of second polymeric material therebetween have an optical thickness of not more than 0.09 micrometers, optical thicknesses between 0.09 micrometers and 0.45 micrometers, or optical thicknesses not less than 0.45 micrometers.
  • the first and second polymeric material have refractive indices which differ by at least 0.03.
  • the ribbons 62 themselves may comprise a microlayer structure of alternating first and second polymeric materials, with the individual layers having optical thicknesses of not more than 0.09 micrometers, between 0.09 micrometers and 0.45 micrometers, or not less than 0.45 micrometers as desired.
  • the first and second polymeric material have refractive indices which differ by at least 0.03.
  • the polymeric body will comprise multiple overlapping layers of ribbons having layers of alternating first and second polymeric materials embedded in a matrix of a third polymer.
  • the microlayer stream may be created by using the techniques taught in the aforementioned US-A-3,565,985, US-A-3,759,647, US-A-3,773,882, and US-A-3,884,606.
  • the controlled ribbon-like morphology of the polymeric body of the present invention results in a structure having many useful anisotropic properties. Because the many overlapping ribbons are continuous in the extrusion direction of the body, but discontinuous in the transverse direction, tensile properties of the body may be high in the extrusion direction but lower in the transverse direction if suitable polymers are selected. If ribbons are made from liquid crystalline polymers such as those polymers available from Celanese Corporation under the designation Vectra, very high tensile properties in the extrusion direction are obtained. Further, the matrix polymer embedding the ribbons prevents catastrophic delamination.
  • a polymeric body having ribbons which are lamellar in cross section may also be produced by positioning a reciprocating valve or feed plate 70 ahead of first dividing means 40 in die body 30.
  • Reciprocating feed plate 70 comprises a series of alternating holes 72 and slots 74 as best seen in Fig. 5.
  • Holes 72 are in communication with the first polymer stream in plenum 32.
  • Slots 74 are in communication with the second polymer stream entering intermediate plenum 34 through conduit 76.
  • passages 46 are alternately fed "slugs" of the first and second polymer.
  • the first polymeric material may be made to be discontinuous in all major planar directions of the body, producing layers of platelet-like elements in a continuous matrix of a second polymer.
  • a stationary feed plate 70 (shown in Fig. 7A) is positioned at the outlet end of passages 48.
  • Reciprocating feed plate 73 (shown in Fig. 7B) is positioned behind stationary feed plate 70.
  • Reciprocating feed plate 73 comprises a series of staggered openings which alternately communicate with either the encapsulated tubes of polymer from holes 72 or polymer from slots 74 in feed plate 70.
  • a stationary plate 78 (shown in Fig. 7C), having rows of holes 80 is located behind reciprocating feed plate 73.
  • a first polymer is fed from plenum 32 into passages 46 and then encapsulated by a second polymer introduced through conduit 15 into intermediate plenum 34.
  • rows of the first polymer encapsulated within the second polymer are alternately spaced between slots communicating with a third polymer source, where the third polymer may be the same as or different from the second polymer.
  • stationary feed plate 70 comprises alternating rows of holes 72 and vertical slots 74. Holes 72 communicate with the first polymer stream encapsulated in the second polymer while slots 74 communicate with a source of third polymer (which can be the same as the second polymer) through conduit 76. Flow of the polymer through reciprocating plate 73 produces alternating "slugs" of encapsulated first polymer with a second or third polymer.
  • discontinuous slugs then flow through manipulating section 20 where the number of layers is further multiplied, or directly to shaping die 22.
  • the first polymer is deformed into discontinuous platelet-like elements within a matrix polymer.
  • the encapsulating layer of the second polymer acts as a lubricating boundary layer so that the first polymer maintains substantially plug flow through the system.
  • the resulting polymeric body is illustrated in Fig. 8, with many layers of overlapping platelets 82 of the first polymer contained within a matrix 84 of the second polymer. As can be seen, the platelets are discontinuous along planes both parallel to and transverse to the major surfaces of the body.
  • the controlled platelet-like morphology produced by this embodiment of the invention has several utilities. Where the polymeric body produced is one which is reflective, light is reflected from the many interfaces of the overlapping platelets much like the scales of a silvery appearing fish.
  • Imperfect adhesion between the first and second polymers does not necessarily adversely affect the physical or optical properties of the body.
  • a polymeric reflective body prepared from a polystyrene (R.I. 1.59) matrix which contains platelets of polymethyl methacrylate (R.I. 1.49) does not catastrophically delaminate even though in a laminate having continuous layers of the two polymers, moderate flexing will produce delamination. Because of the continuous matrix of the second polymer, the body maintains its integrity.
  • air, or other gases or liquids may be introduced into the polymer melt forming the platelets.
  • the matrix polymer is elastomeric, the polymer making up the platelets can be nonelastomeric and yet the polymeric body will still possess elastomeric properties in all directions.
  • the polymer used to form the platelets may be one which is a barrier to gases and/or liquids. The many layers of overlapping platelets may provide an excellent barrier to gases because of the tortuous path to gas permeation.
  • the platelets can themselves be multilayered either by feeding a microlayer stream of alternating layers of diverse polymers into plenum 32 or by positioning reciprocating feed plates or valves, as shown in Fig. 4 and Fig. 6, at both the inlet and outlet ends of passages 46.
  • the method of the present invention uniquely provides for controlled placement and dispersion of one component in a continuous matrix of another.
  • the size and placement of the platelets is managed by the mechanical means described above.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Composite Materials (AREA)
  • Ophthalmology & Optometry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Materials For Medical Uses (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (14)

  1. Lamellarer Polymerkörper mit wenigstens ersten und zweiten Hauptoberflächen, wobei der Körper eine Vielzahl von diskontinuierlichen individuellen Schichten innerhalb einer Matrix aus Polymermaterial aufweist, wobei jede individuelle Schicht entweder ein erstes Polymermaterial oder eine Vielzahl von abwechselnden Schichten des ersten Polymermaterials und eines zweiten Polymermaterials enthält und die Hauptgrenzflächen der individuellen Schichten im wesentlichen parallel zu den Hauptoberflächen des Körpers ausgerichtet sind und das Polymermaterial der Matrix, das erste und, falls vorhanden, das zweite Polymermaterial voneinander verschieden sind.
  2. Lamellarer Polymerkörper nach Anspruch 1, dadurch gekennzeichnet, daß die Zahl der diskontinuierlichen individuellen Schichten ausreichend ist, um einen reflektierenden Körper auszubilden, der mindestens 30 % des auf den Körper einfallenden Lichtes reflektiert, und wobei das erste und, falls vorhanden, das zweite Polymermaterial oder das erste Polymermaterial und das Polymermaterial der Matrix sich durch einen Brechungsindex von mindestens 0,03 voneinander unterscheiden.
  3. Lamellarer Polymerkörper nach Anspruch 2, dadurch gekennzeichnet, daß die diskontinuierlichen individuellen Schichten aus dem ersten Polymermaterial bestehen und das erste und das Polymermaterial der Matrix sich durch einen Brechungsindex von mindestens 0,03 voneinander unterscheiden.
  4. Lamellarer Polymerkörper nach Anspruch 2, dadurch gekennzeichnet, daß die diskontinuierlichen individuellen Schichten abwechselnd aus ersten und zweiten Polymermaterialien bestehen und die ersten und zweiten Polymermaterialien sich durch einen Brechungsindex von mindestens 0,03 voneinander unterscheiden.
  5. Lamellarer Polymerkörper nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, daß eine ausreichende Zahl von Schichten des ersten Polymermaterials und, falls vorhanden, Schichten des zweiten Polymermaterials und die Teile des zwischen die diskontinuierlichen individuellen Schichten eingelagerten Polymermaterials der Matrix eine optische Dichte zwischen 0,09 µm und 0,45 µm aufweisen, so daß der Körper ein farbiges und/oder silbrig irisierendes Aussehen aufweist.
  6. Lamellarer Polymerkörper nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, daß mindestens 75 % der individuellen Schichten des ersten Polymermaterials und, falls vorhanden, von Schichten des zweiten Polymermaterials und die Teile des zwischen die diskontinuierlichen individuellen Schichten eingelagerten Polymermaterials der Matrix eine optische Dichte von mindestens 0,45 µm aufweisen, so daß der Körper ein gleichmäßig reflektierendes, metallisches Aussehen aufweist.
  7. Lamellarer Polymerkörper nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, daß eine ausreichende Zahl von Schichten des ersten Polymermaterials und, falls vorhanden, Schichten des zweiten Polymermaterials und die Teile des zwischen die diskontinuierlichen individuellen Schichten eingelagerten Polymermaterials der Matrix eine optische Dichte von höchstens 0,09 µm oder wenigstens 0,45 µm aufweisen, so daß kein mit bloßem Auge wahrnehmbares Irisieren reflektiert wird.
  8. Lamellarer Polymerkörper nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Polymermaterial der Matrix elastomer ist.
  9. Lamellarer Polymerkörper nach Anspruch 8, dadurch gekennzeichnet, daß das erste und, falls vorhanden, das zweite Polymermaterial ebenfalls elastomer sind.
  10. Lamellarer Polymerkörper nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die diskontinuierlichen individuellen Schichten in einer ersten, zu einer der Hauptoberflächen des Körpers parallelen Ebene im wesentlichen durchgehend und in einer die erste Ebene durchquerenden zweiten Ebene unterbrochen sind.
  11. Lamellarer Polymerkörper nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die diskontinuierlichen individuellen Schichten entlang Ebenen, die parallel zu einer der Hauptoberflächen des Körpers verlaufen oder diese durchqueren, im wesentlichen unterbrochen sind.
  12. Lamellarer Polymerkörper nach einem der Ansprüche 1 bis 7, 10 und 11, dadurch gekennzeichnet, daß das erste Polymermaterial Polymethylmethacrylat und das Polymermaterial der Matrix Polystyrol ist.
  13. Lamellarer Polymerkörper nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß eine Flüssigkeit an einer Vielzahl der Hauptgrenzflächen der individuellen Schichten vorhanden ist.
  14. Lamellarer Polymerkörper nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das erste Polymermaterial ein gasdichtes Material ist.
EP92904514A 1991-01-22 1991-12-18 Lamellenartig polymerer körper und verfahren zu seiner herstellung Expired - Lifetime EP0647183B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US643611 1991-01-22
US07/643,611 US5217794A (en) 1991-01-22 1991-01-22 Lamellar polymeric body
PCT/US1991/009597 WO1992012857A1 (en) 1991-01-22 1991-12-18 Lamellar polymeric body and method of production

Publications (3)

Publication Number Publication Date
EP0647183A4 EP0647183A4 (de) 1993-11-08
EP0647183A1 EP0647183A1 (de) 1995-04-12
EP0647183B1 true EP0647183B1 (de) 1998-09-02

Family

ID=24581559

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92904514A Expired - Lifetime EP0647183B1 (de) 1991-01-22 1991-12-18 Lamellenartig polymerer körper und verfahren zu seiner herstellung

Country Status (13)

Country Link
US (2) US5217794A (de)
EP (1) EP0647183B1 (de)
JP (1) JP2993736B2 (de)
KR (1) KR930703147A (de)
CN (1) CN1063449A (de)
AT (1) ATE170455T1 (de)
AU (1) AU1151392A (de)
CA (1) CA2100061A1 (de)
DE (1) DE69130118T2 (de)
FI (1) FI933294A (de)
MX (1) MX9200263A (de)
NO (1) NO932637D0 (de)
WO (1) WO1992012857A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7887660B2 (en) 2004-10-22 2011-02-15 Dow Global Technologies Inc. Composite pipes and method making same

Families Citing this family (241)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910854A (en) 1993-02-26 1999-06-08 Donnelly Corporation Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices
US5360659A (en) * 1993-05-24 1994-11-01 The Dow Chemical Company Two component infrared reflecting film
US5946431A (en) * 1993-07-30 1999-08-31 Molecular Dynamics Multi-functional photometer with movable linkage for routing light-transmitting paths using reflective surfaces
US6025897A (en) 1993-12-21 2000-02-15 3M Innovative Properties Co. Display with reflective polarizer and randomizing cavity
US5882774A (en) 1993-12-21 1999-03-16 Minnesota Mining And Manufacturing Company Optical film
US6498683B2 (en) * 1999-11-22 2002-12-24 3M Innovative Properties Company Multilayer optical bodies
US6804058B1 (en) 1993-12-21 2004-10-12 3M Innovative Properties Company Electroluminescent light source and display incorporating same
CN1046664C (zh) * 1993-12-21 1999-11-24 美国3M公司 多层聚合物薄膜,其制造方法及其应用
US6096375A (en) * 1993-12-21 2000-08-01 3M Innovative Properties Company Optical polarizer
US20070091230A1 (en) * 1993-12-21 2007-04-26 3M Innovative Properties Company Display incorporating reflective polarizer
US5828488A (en) * 1993-12-21 1998-10-27 Minnesota Mining And Manufacturing Co. Reflective polarizer display
US6101032A (en) * 1994-04-06 2000-08-08 3M Innovative Properties Company Light fixture having a multilayer polymeric film
US5668663A (en) 1994-05-05 1997-09-16 Donnelly Corporation Electrochromic mirrors and devices
JP2928108B2 (ja) * 1994-11-17 1999-08-03 三菱レイヨン株式会社 複合樹脂シートの製造装置及びその製造方法
US6630238B2 (en) 1995-02-16 2003-10-07 3M Innovative Properties Company Blended pressure-sensitive adhesives
US6063838A (en) * 1995-02-16 2000-05-16 3M Innovative Properties Company Blended pressure-sensitive adhesives
US6632522B1 (en) 1995-02-16 2003-10-14 3M Innovative Properties Company Blended pressure-sensitive adhesives
US5500173A (en) * 1995-02-17 1996-03-19 Basf Corporation Method of making molded muticomponent articles using a thin plate flow distributor
US5751388A (en) 1995-04-07 1998-05-12 Honeywell Inc. High efficiency polarized display
US6891563B2 (en) 1996-05-22 2005-05-10 Donnelly Corporation Vehicular vision system
DE69626018D1 (de) 1995-06-26 2003-03-06 Minnesota Mining & Mfg Lichtstreuender klebstoff
WO1997001726A1 (en) 1995-06-26 1997-01-16 Minnesota Mining And Manufacturing Company Backlight system with multilayer optical film reflector
EP0871923A1 (de) 1995-06-26 1998-10-21 Minnesota Mining And Manufacturing Company Transflektive anzeige mit reflektierendem polarisierendem transflektor
IL122244A0 (en) 1995-06-26 1998-04-05 Minnesota Mining & Mfg Multilayer polymer film with additional coatings or layers
US5699188A (en) * 1995-06-26 1997-12-16 Minnesota Mining And Manufacturing Co. Metal-coated multilayer mirror
BR9609392A (pt) 1995-06-26 1999-05-18 Minnesota Mining & Mfg Dispositivo de multicamadas transparente
US6080467A (en) * 1995-06-26 2000-06-27 3M Innovative Properties Company High efficiency optical devices
US6737154B2 (en) 1995-06-26 2004-05-18 3M Innovative Properties Company Multilayer polymer film with additional coatings or layers
US6088067A (en) * 1995-06-26 2000-07-11 3M Innovative Properties Company Liquid crystal display projection system using multilayer optical film polarizers
DE69626124T2 (de) * 1995-06-26 2003-10-09 Minnesota Mining & Mfg Diffus reflektierende mehrschicht-polarisatoren und spiegel
US5686979A (en) * 1995-06-26 1997-11-11 Minnesota Mining And Manufacturing Company Optical panel capable of switching between reflective and transmissive states
US5610455A (en) * 1995-06-29 1997-03-11 Minnesota Mining And Manufacturing Company Electret containing syndiotactic vinyl aromatic polymer
CN1100472C (zh) * 1995-08-11 2003-01-29 美国3M公司 使用多层光学薄膜的场致发光灯
EP0789857B1 (de) * 1995-08-23 2004-06-30 Koninklijke Philips Electronics N.V. Beleuchtungssystem für eine flachtafel-bildanzeigevorrichtung
JPH10509537A (ja) * 1995-09-22 1998-09-14 フィリップス エレクトロニクス ネムローゼ フェンノートシャップ フラットパネル画像表示装置
DE69634849T2 (de) * 1995-09-25 2006-05-18 Koninklijke Philips Electronics N.V. Elektrolumineszentes beleuchtungssystem und flachtafelbildanzeigevorrichtung mit einem solchen system
DE19680995D2 (de) * 1995-11-23 1999-01-28 Roehm Gmbh Lichtleitplatten
AU713583B2 (en) 1996-02-29 1999-12-02 Minnesota Mining And Manufacturing Company Brightness enhancement film
US5783120A (en) * 1996-02-29 1998-07-21 Minnesota Mining And Manufacturing Company Method for making an optical film
US5867316A (en) * 1996-02-29 1999-02-02 Minnesota Mining And Manufacturing Company Multilayer film having a continuous and disperse phase
US5825543A (en) * 1996-02-29 1998-10-20 Minnesota Mining And Manufacturing Company Diffusely reflecting polarizing element including a first birefringent phase and a second phase
JP4221522B2 (ja) * 1996-02-29 2009-02-12 スリーエム カンパニー 共一連続相を有する光学薄膜
US5968666A (en) * 1996-03-08 1999-10-19 3M Innovative Properties Company Multilayer polyester film
US5759467A (en) * 1996-03-08 1998-06-02 Minnesota Mining And Manufacturing Company Method for making multilayer polyester film
US5783283A (en) * 1996-03-08 1998-07-21 Minnesota Mining And Manufacturing Company Multilayer polyester film with a low coefficient of friction
US5795528A (en) * 1996-03-08 1998-08-18 Minnesota Mining And Manufacturing Company Method for making a multilayer polyester film having a low coefficient of friction
US5661839A (en) * 1996-03-22 1997-08-26 The University Of British Columbia Light guide employing multilayer optical film
US5808798A (en) * 1996-03-27 1998-09-15 Minnesota Mining And Manufacturing Co. Nonpolarizing beamsplitter
US5808794A (en) 1996-07-31 1998-09-15 Weber; Michael F. Reflective polarizers having extended red band edge for controlled off axis color
US5976424A (en) * 1996-07-31 1999-11-02 Minnesota Mining And Manufacturing Company Method for making multilayer optical films having thin optical layers
JPH1078511A (ja) * 1996-09-04 1998-03-24 Hitachi Ltd 偏光分離器、偏光変換素子およびそれを用いた液晶表示装置
US8294975B2 (en) 1997-08-25 2012-10-23 Donnelly Corporation Automotive rearview mirror assembly
US6326613B1 (en) 1998-01-07 2001-12-04 Donnelly Corporation Vehicle interior mirror assembly adapted for containing a rain sensor
US6124886A (en) 1997-08-25 2000-09-26 Donnelly Corporation Modular rearview mirror assembly
US6172613B1 (en) 1998-02-18 2001-01-09 Donnelly Corporation Rearview mirror assembly incorporating vehicle information display
US6106922A (en) * 1997-10-03 2000-08-22 3M Innovative Company Coextruded mechanical fastener constructions
US6627300B1 (en) 1997-10-12 2003-09-30 3M Innovative Properties Company Optical device containing polymeric material domains having different degrees of randomness
US6486997B1 (en) 1997-10-28 2002-11-26 3M Innovative Properties Company Reflective LCD projection system using wide-angle Cartesian polarizing beam splitter
US7023602B2 (en) * 1999-05-17 2006-04-04 3M Innovative Properties Company Reflective LCD projection system using wide-angle Cartesian polarizing beam splitter and color separation and recombination prisms
US5999316A (en) 1997-12-06 1999-12-07 3M Innovative Properties Company Light valve with rotating polarizing element
US8288711B2 (en) 1998-01-07 2012-10-16 Donnelly Corporation Interior rearview mirror system with forwardly-viewing camera and a control
US6445287B1 (en) 2000-02-28 2002-09-03 Donnelly Corporation Tire inflation assistance monitoring system
US6926952B1 (en) 1998-01-13 2005-08-09 3M Innovative Properties Company Anti-reflective polymer constructions and method for producing same
US6049419A (en) 1998-01-13 2000-04-11 3M Innovative Properties Co Multilayer infrared reflecting optical body
US6157486A (en) * 1998-01-13 2000-12-05 3M Innovative Properties Company Retroreflective dichroic reflector
US6179948B1 (en) 1998-01-13 2001-01-30 3M Innovative Properties Company Optical film and process for manufacture thereof
US6531230B1 (en) 1998-01-13 2003-03-11 3M Innovative Properties Company Color shifting film
US6967778B1 (en) 1998-01-13 2005-11-22 3M Innovative Properties Co. Optical film with sharpened bandedge
US5999317A (en) * 1998-01-13 1999-12-07 3M Innovative Properties Company Toy mirror with transmissive image mode
US6053795A (en) * 1998-01-13 2000-04-25 3M Innovative Properties Company Toy having image mode and changed image mode
US6082876A (en) 1998-01-13 2000-07-04 3M Innovative Properties Company Hand-holdable toy light tube with color changing film
US6207260B1 (en) 1998-01-13 2001-03-27 3M Innovative Properties Company Multicomponent optical body
US6012820A (en) * 1998-01-13 2000-01-11 3M Innovative Properties Compnay Lighted hand-holdable novelty article
US6024455A (en) * 1998-01-13 2000-02-15 3M Innovative Properties Company Reflective article with concealed retroreflective pattern
US6569515B2 (en) 1998-01-13 2003-05-27 3M Innovative Properties Company Multilayered polymer films with recyclable or recycled layers
US6111697A (en) * 1998-01-13 2000-08-29 3M Innovative Properties Company Optical device with a dichroic polarizer and a multilayer optical film
DE69924354T2 (de) * 1998-01-13 2006-03-09 Minnesota Mining & Manufacturing Company, St. Paul Modifizierte copolyester und verbesserte reflektierende mehrschichtfolie
US6120026A (en) * 1998-01-13 2000-09-19 3M Innovative Properties Co. Game with privacy material
US6045894A (en) * 1998-01-13 2000-04-04 3M Innovative Properties Company Clear to colored security film
US6113811A (en) 1998-01-13 2000-09-05 3M Innovative Properties Company Dichroic polarizing film and optical polarizer containing the film
US6788463B2 (en) * 1998-01-13 2004-09-07 3M Innovative Properties Company Post-formable multilayer optical films and methods of forming
US6157490A (en) * 1998-01-13 2000-12-05 3M Innovative Properties Company Optical film with sharpened bandedge
US6808658B2 (en) * 1998-01-13 2004-10-26 3M Innovative Properties Company Method for making texture multilayer optical films
EP1047732B1 (de) 1998-01-13 2002-09-11 Minnesota Mining And Manufacturing Company Glitzernde filmpartikel mit farbveränderung
US6329925B1 (en) 1999-11-24 2001-12-11 Donnelly Corporation Rearview mirror assembly with added feature modular display
US6477464B2 (en) 2000-03-09 2002-11-05 Donnelly Corporation Complete mirror-based global-positioning system (GPS) navigation solution
US6693517B2 (en) 2000-04-21 2004-02-17 Donnelly Corporation Vehicle mirror assembly communicating wirelessly with vehicle accessories and occupants
US6256146B1 (en) * 1998-07-31 2001-07-03 3M Innovative Properties Post-forming continuous/disperse phase optical bodies
US6749427B1 (en) * 1998-07-31 2004-06-15 3M Innovative Properties Company Dental articles including post-formable multilayer optical films
US6005713A (en) * 1998-08-21 1999-12-21 3M Innovative Properties Company Multilayer polarizer having a continuous and disperse phase
US6082025A (en) * 1998-09-11 2000-07-04 Nike, Inc. Flexible membranes
CA2343816C (en) 1998-09-11 2009-04-14 Nike International Ltd. Flexible membranes
US6127026A (en) * 1998-09-11 2000-10-03 Nike, Inc. Flexible membranes
US6208466B1 (en) 1998-11-25 2001-03-27 3M Innovative Properties Company Multilayer reflector with selective transmission
US6187233B1 (en) 1998-12-15 2001-02-13 Guardian Automotive Trim, Inc. Automotive trim with clear top coat and method of making same
US6319438B1 (en) 1998-12-15 2001-11-20 Guardian Automotive Trim, Inc. Extruded automotive trim and method of making same
US6455140B1 (en) 1999-01-13 2002-09-24 3M Innovative Properties Company Visible mirror film glitter
US6322236B1 (en) 1999-02-09 2001-11-27 3M Innovative Properties Company Optical film with defect-reducing surface and method for making same
US6381068B1 (en) 1999-03-19 2002-04-30 3M Innovative Properties Company Reflective projection screen and projection system
US6515785B1 (en) 1999-04-22 2003-02-04 3M Innovative Properties Company Optical devices using reflecting polarizing materials
US6187845B1 (en) 1999-05-03 2001-02-13 Ciba Specialty Chemicals Corporation Stabilized adhesive compositions containing highly soluble, red-shifted, photostable benzotriazole UV absorbers and laminated articles derived therefrom
US6268415B1 (en) 1999-05-03 2001-07-31 Ciba Specialty Chemicals Corporation Stabilized adhesive compositions containing highly soluble, photostable benzotriazole UV absorbers and laminated articles derived therefrom
US6245915B1 (en) 1999-05-03 2001-06-12 Ciba Specialty Chemicals Corporation Asymmetrical bisbenzotriazoles substituted by a perfluoroalkyl moiety
US6191199B1 (en) 1999-05-03 2001-02-20 Ciba Speciatly Chemicals Corporation Stabilized adhesive compositions containing highly soluble, high extinction photostable hydroxyphenyl-s-triazine UV absorbers and laminated articles derived therefrom
US6952310B1 (en) * 1999-05-12 2005-10-04 Nitto Denko Corporation Light pipe and polarized-light source
US6407862B2 (en) 1999-05-14 2002-06-18 3M Innovative Properties Company Electronic projection system with polymeric film optical components
US6972813B1 (en) * 1999-06-09 2005-12-06 3M Innovative Properties Company Optical laminated bodies, lighting equipment and area luminescence equipment
US6699426B1 (en) * 1999-06-15 2004-03-02 National Gypsum Properties, Llc. Gypsum wallboard core, and method and apparatus for making the same
US6447875B1 (en) 1999-07-30 2002-09-10 3M Innovative Properties Company Polymeric articles having embedded phases
US6927315B1 (en) * 1999-07-30 2005-08-09 3M Innovative Properties Company Adhesive composite having distinct phases
US6239907B1 (en) 1999-09-03 2001-05-29 3M Innovative Properties Company Rear projection screen using birefringent optical film for asymmetric light scattering
WO2001022129A1 (en) 1999-09-20 2001-03-29 3M Innovative Properties Company Optical films having at least one particle-containing layer
US6449093B2 (en) 1999-10-12 2002-09-10 3M Innovative Properties Company Optical bodies made with a birefringent polymer
US6654170B1 (en) 1999-10-12 2003-11-25 3M Innovative Properties Company Optical device having continuous and disperse phases
US6673275B1 (en) 1999-10-12 2004-01-06 3M Innovative Properties Company Method for making optical devices from homopolymers
US7195727B2 (en) * 1999-10-13 2007-03-27 Guardian Industries Corp. Extruded automotive trim and method of making same
US6264336B1 (en) 1999-10-22 2001-07-24 3M Innovative Properties Company Display apparatus with corrosion-resistant light directing film
US6590711B1 (en) 2000-04-03 2003-07-08 3M Innovative Properties Co. Light directing construction having corrosion resistant feature
US7370983B2 (en) 2000-03-02 2008-05-13 Donnelly Corporation Interior mirror assembly with display
WO2001064481A2 (en) 2000-03-02 2001-09-07 Donnelly Corporation Video mirror systems incorporating an accessory module
US7004593B2 (en) 2002-06-06 2006-02-28 Donnelly Corporation Interior rearview mirror system with compass
US7167796B2 (en) 2000-03-09 2007-01-23 Donnelly Corporation Vehicle navigation system for use with a telematics system
US6590707B1 (en) 2000-03-31 2003-07-08 3M Innovative Properties Company Birefringent reflectors using isotropic materials and form birefringence
JP2003532752A (ja) 2000-04-13 2003-11-05 スリーエム イノベイティブ プロパティズ カンパニー 光安定性の製品
DE50004562D1 (de) * 2000-05-03 2004-01-08 Swiss Caps Rechte & Lizenzen Verfahren und Vorrichtung zum Herstellen eines flexiblen Bandes aus wenigstens zwei verchiedenen, bei Wärmezufuhr fliessfähigen Massen
WO2002016976A2 (en) 2000-08-21 2002-02-28 3M Innovative Properties Company Loss enhanced reflective optical filters
US6727313B2 (en) 2001-01-17 2004-04-27 3M Innovative Properties Company Polymeric compositions and articles with anisotropic light scattering and methods of making and using
US6819486B2 (en) * 2001-01-17 2004-11-16 3M Innovative Properties Company Projection screen having elongated structures
US7581859B2 (en) 2005-09-14 2009-09-01 Donnelly Corp. Display device for exterior rearview mirror
WO2002062623A2 (en) 2001-01-23 2002-08-15 Donnelly Corporation Improved vehicular lighting system for a mirror assembly
US7255451B2 (en) 2002-09-20 2007-08-14 Donnelly Corporation Electro-optic mirror cell
US6506480B2 (en) 2001-02-16 2003-01-14 3M Innovative Properties Company Color shifting film with a plurality of fluorescent colorants
US6534158B2 (en) 2001-02-16 2003-03-18 3M Innovative Properties Company Color shifting film with patterned fluorescent and non-fluorescent colorants
US6573963B2 (en) 2001-02-22 2003-06-03 3M Innovativeproperties Company Cholesteric liquid crystal optical bodies and methods of manufacture
US6917399B2 (en) 2001-02-22 2005-07-12 3M Innovative Properties Company Optical bodies containing cholesteric liquid crystal material and methods of manufacture
US6797201B2 (en) * 2001-04-20 2004-09-28 Procaps S.A. Multicolor gelatin ribbons and manufacture of soft gelatin products
US6876427B2 (en) 2001-09-21 2005-04-05 3M Innovative Properties Company Cholesteric liquid crystal optical bodies and methods of manufacture and use
US6837698B2 (en) * 2001-12-19 2005-01-04 3M Innovative Properties Company Multilayer coextrusion die and method
US6949283B2 (en) * 2001-12-19 2005-09-27 3M Innovative Properties Company Polymeric coextruded multilayer articles
NZ534795A (en) * 2002-03-04 2007-01-26 Rasmussen O B Crosslaminate of oriented films, method of manufacturing same, and coextrusion die suitable in the process
US6918674B2 (en) 2002-05-03 2005-07-19 Donnelly Corporation Vehicle rearview mirror system
US6991695B2 (en) * 2002-05-21 2006-01-31 3M Innovative Properties Company Method for subdividing multilayer optical film cleanly and rapidly
US7095009B2 (en) * 2002-05-21 2006-08-22 3M Innovative Properties Company Photopic detector system and filter therefor
US7396493B2 (en) * 2002-05-21 2008-07-08 3M Innovative Properties Company Multilayer optical film with melt zone to control delamination
US7329013B2 (en) 2002-06-06 2008-02-12 Donnelly Corporation Interior rearview mirror system with compass
US7198744B2 (en) * 2002-08-06 2007-04-03 The Goodyear Tire & Rubber Company Preparation of co-extruded multi-layered rubber composite and use as component of a tire
US7310177B2 (en) 2002-09-20 2007-12-18 Donnelly Corporation Electro-optic reflective element assembly
EP1543358A2 (de) 2002-09-20 2005-06-22 Donnelly Corporation Spiegelreflexionselementbaugruppe
AU2003284335A1 (en) * 2002-10-24 2004-05-13 3M Innovative Properties Company Methods of making high gain optical devices having a continuous and dispersive phase
US20040219338A1 (en) * 2003-05-01 2004-11-04 Hebrink Timothy J. Materials, configurations, and methods for reducing warpage in optical films
US20040219366A1 (en) * 2003-05-02 2004-11-04 Johnson John R. Bright formable metalized film laminate
US7289037B2 (en) 2003-05-19 2007-10-30 Donnelly Corporation Mirror assembly for vehicle
US7446924B2 (en) 2003-10-02 2008-11-04 Donnelly Corporation Mirror reflective element assembly including electronic component
US7308341B2 (en) 2003-10-14 2007-12-11 Donnelly Corporation Vehicle communication system
US7097908B2 (en) * 2003-10-20 2006-08-29 Arkema Polyamide/polyurethane multilayer structures for decorated articles
FR2861014A1 (fr) * 2003-10-20 2005-04-22 Atofina Structures multicouches polyamide/polyurethande pour articles decores
US7019905B2 (en) * 2003-12-30 2006-03-28 3M Innovative Properties Company Multilayer reflector with suppression of high order reflections
DE102004021494B4 (de) * 2004-04-30 2006-04-06 Man Roland Druckmaschinen Ag Vorrichtung zum Auf- und Abziehen einer Hülse
US20060159888A1 (en) * 2004-10-29 2006-07-20 Hebrink Timothy J Optical films incorporating cyclic olefin copolymers
KR101165487B1 (ko) * 2004-10-29 2012-07-13 쓰리엠 이노베이티브 프로퍼티즈 컴파니 시클릭 올레핀 공중합체를 혼입한 광학 필름
US7329465B2 (en) * 2004-10-29 2008-02-12 3M Innovative Properties Company Optical films incorporating cyclic olefin copolymers
US20060093809A1 (en) * 2004-10-29 2006-05-04 Hebrink Timothy J Optical bodies and methods for making optical bodies
US20060193578A1 (en) * 2005-02-28 2006-08-31 Ouderkirk Andrew J Composite polymeric optical films with co-continuous phases
US7356229B2 (en) * 2005-02-28 2008-04-08 3M Innovative Properties Company Reflective polarizers containing polymer fibers
US7356231B2 (en) * 2005-02-28 2008-04-08 3M Innovative Properties Company Composite polymer fibers
US7362943B2 (en) * 2005-02-28 2008-04-22 3M Innovative Properties Company Polymeric photonic crystals with co-continuous phases
US7386212B2 (en) * 2005-02-28 2008-06-10 3M Innovative Properties Company Polymer photonic crystal fibers
US7406239B2 (en) * 2005-02-28 2008-07-29 3M Innovative Properties Company Optical elements containing a polymer fiber weave
EP1877696A1 (de) * 2005-03-12 2008-01-16 3M Innovative Properties Company Beleuchtungsvorrichtung und herstellungsverfahren dafür
ATE411161T1 (de) 2005-04-06 2008-10-15 3M Innovative Properties Co Optische körper mit rauen abziehbaren grenzschichten und asymmetrischen oberflächenstrukturen
US20060227421A1 (en) 2005-04-06 2006-10-12 Stover Carl A Optical bodies including strippable boundary layers
US9709700B2 (en) * 2005-04-06 2017-07-18 3M Innovative Properties Company Optical bodies including rough strippable boundary layers
ATE517368T1 (de) 2005-05-16 2011-08-15 Donnelly Corp Fahrzeugspiegelanordnung mit zeichen am reflektierenden teil
US7568902B2 (en) * 2005-06-08 2009-08-04 Eastern Petroleum Sdn Bhd Bitumen bale capsule, capsule dispenser, and bale strip former for viscous bitumen products
US7180779B2 (en) * 2005-07-11 2007-02-20 Atmel Corporation Memory architecture with enhanced over-erase tolerant control gate scheme
EP1949666B1 (de) 2005-11-01 2013-07-17 Magna Mirrors of America, Inc. Innen-rückspiegel mit display
US20070154683A1 (en) * 2005-12-29 2007-07-05 3M Innovative Properties Company Microstriped film
US20070281157A1 (en) * 2006-06-05 2007-12-06 Laney Thomas M Reflective polarizer, fiber, and process for making
US7583440B2 (en) * 2006-06-05 2009-09-01 Skc Haas Display Films Co., Ltd. Diffusely-reflecting polarizer having nearly isotropic continuous phase
US20070281143A1 (en) * 2006-06-05 2007-12-06 Aylward Peter T Diffusely-reflecting element and method of making
KR101442275B1 (ko) 2006-08-01 2014-09-22 쓰리엠 이노베이티브 프로퍼티즈 컴파니 조명 장치 및 차량 창유리
US7773834B2 (en) 2006-08-30 2010-08-10 3M Innovative Properties Company Multilayer polarizing fibers and polarizers using same
US7599592B2 (en) * 2006-08-30 2009-10-06 3M Innovative Properties Company Polymer fiber polarizers with aligned fibers
US20080057277A1 (en) * 2006-08-30 2008-03-06 3M Innovative Properties Company Polymer fiber polarizers
US8525402B2 (en) 2006-09-11 2013-09-03 3M Innovative Properties Company Illumination devices and methods for making the same
US8581393B2 (en) * 2006-09-21 2013-11-12 3M Innovative Properties Company Thermally conductive LED assembly
US20080271739A1 (en) 2007-05-03 2008-11-06 3M Innovative Properties Company Maintenance-free respirator that has concave portions on opposing sides of mask top section
US9770611B2 (en) 2007-05-03 2017-09-26 3M Innovative Properties Company Maintenance-free anti-fog respirator
US20080295327A1 (en) * 2007-06-01 2008-12-04 3M Innovative Properties Company Flexible circuit
CN101589183B (zh) 2007-06-19 2011-12-07 日东电工株式会社 偏振光纤、偏振元件、偏振片、层叠光学薄膜以及图像显示装置
US20090072434A1 (en) * 2007-09-14 2009-03-19 Kotaro Takita Coextrusion die and manifold system therefor
JP4354526B2 (ja) * 2007-10-31 2009-10-28 三井・デュポンポリケミカル株式会社 粘着フィルム又はシート
WO2009113422A1 (ja) 2008-03-14 2009-09-17 東レ株式会社 積層フィルム
US8154418B2 (en) 2008-03-31 2012-04-10 Magna Mirrors Of America, Inc. Interior rearview mirror system
EP2113366A1 (de) 2008-04-24 2009-11-04 Tonen Chemical Corporation Extrusionsdüse und Verteilersystem dafür
EP2113362A1 (de) 2008-04-24 2009-11-04 Tonen Chemical Corporation Koextrusionsdüse und Verteilersystem dafür
EP2113363A1 (de) 2008-04-24 2009-11-04 Tonen Chemical Corporation Verfahren zum Schutz eines Extrudats vor Prozesskondensation
EP2113365A1 (de) 2008-04-24 2009-11-04 Tonen Chemical Corporation Extrusionsdüse mit verbessertem Querstromverteiler
ES2550013T3 (es) * 2008-05-06 2015-11-03 Hid Global Gmbh Laminado funcional
US9487144B2 (en) 2008-10-16 2016-11-08 Magna Mirrors Of America, Inc. Interior mirror assembly with display
CN102883866B (zh) 2010-05-07 2015-11-25 3M创新有限公司 用于制备多层聚合物薄膜的送料区块
BR112012033226A2 (pt) 2010-06-30 2016-11-16 3M Innovative Properties Co filmes ópticos diufsos reflexivos com redução de birrefringência espacialmente seletiva
US9101956B2 (en) 2010-06-30 2015-08-11 3M Innovative Properties Company Mask processing using films with spatially selective birefringence reduction
WO2012003215A1 (en) 2010-06-30 2012-01-05 3M Innovative Properties Company Retarder film combinations with spatially selective birefringence reduction
US8559779B2 (en) * 2010-10-08 2013-10-15 The Boeing Company Transparent composites with organic fiber
WO2012092534A1 (en) 2010-12-30 2012-07-05 United States Gypsum Company Slurry distribution system and method
US9296124B2 (en) 2010-12-30 2016-03-29 United States Gypsum Company Slurry distributor with a wiping mechanism, system, and method for using same
US9999989B2 (en) * 2010-12-30 2018-06-19 United States Gypsum Company Slurry distributor with a profiling mechanism, system, and method for using same
JP6075787B2 (ja) * 2010-12-30 2017-02-08 ユナイテッド・ステイツ・ジプサム・カンパニー スラリー分配器、システム、およびそれを用いるためのおよび方法
US10076853B2 (en) * 2010-12-30 2018-09-18 United States Gypsum Company Slurry distributor, system, and method for using same
US20140030499A1 (en) * 2011-04-12 2014-01-30 Teijin Limited Oriented laminated film
MX353809B (es) 2011-10-24 2018-01-30 United States Gypsum Co Molde de pieza múltiple y método para elaborar un distribuidor de lechada.
WO2013063073A2 (en) 2011-10-24 2013-05-02 United States Gypsum Company Slurry distributor, system, and method for using same
AU2012328945B2 (en) 2011-10-24 2017-07-20 United States Gypsum Company Multiple-leg discharge boot for slurry distribution
US20130277870A1 (en) * 2012-04-18 2013-10-24 Skc Haas Display Films Co., Ltd. Method of manufacturing a nano-layered light guide plate
US9108218B2 (en) * 2012-04-19 2015-08-18 Nordson Corporation System and method for making multilayer films and a layer multiplication device
KR101930549B1 (ko) * 2012-08-09 2018-12-18 도레이케미칼 주식회사 다층 반사편광자의 제조방법 및 장치
KR101930550B1 (ko) * 2012-08-09 2018-12-18 도레이케미칼 주식회사 중합체가 분산된 반사형 편광자
KR101931377B1 (ko) * 2012-08-09 2018-12-20 도레이케미칼 주식회사 중합체가 분산된 반사형 편광자
KR101930551B1 (ko) * 2012-08-09 2018-12-18 도레이케미칼 주식회사 중합체가 분산된 반사형 편광자
KR101930552B1 (ko) * 2012-08-09 2018-12-18 도레이케미칼 주식회사 폴리머가 분산된 반사 편광자 제조방법 및 장치
KR101931376B1 (ko) * 2012-08-09 2018-12-20 도레이케미칼 주식회사 폴리머가 분산된 반사 편광자 제조방법 및 장치
KR101938892B1 (ko) * 2012-08-09 2019-01-15 도레이케미칼 주식회사 폴리머가 분산된 반사 편광자 제조방법 및 장치
KR101930960B1 (ko) * 2012-08-09 2018-12-19 도레이케미칼 주식회사 일체형 광학필름
KR101938893B1 (ko) * 2012-08-09 2019-01-15 도레이케미칼 주식회사 폴리머가 분산된 반사 편광자 제조방법 및 장치
KR101930553B1 (ko) * 2012-08-09 2019-03-11 도레이케미칼 주식회사 일체형 고휘도 편광필름
MX2015005052A (es) * 2012-10-24 2015-07-17 United States Gypsum Co Distribuidor de lechada con un mecanismo de perfilado, sistema, y metodo de uso del mismo.
EP2994290B1 (de) 2013-05-10 2023-10-04 ABL IP Holding LLC Silikonoptik
US20160154160A1 (en) * 2013-07-10 2016-06-02 Korea Institute Of Industrial Technology Method for manufacturing oriented-fiber composite material, oriented-fiber composite material manufactured thereby, reflective polarizing light film comprising oriented-fiber composite material and method for manufacturing reflective polarizing light film
USD746974S1 (en) 2013-07-15 2016-01-05 3M Innovative Properties Company Exhalation valve flap
AU2014290207B2 (en) 2013-07-15 2017-05-11 3M Innovative Properties Company Respirator having optically active exhalation valve
US10059033B2 (en) 2014-02-18 2018-08-28 United States Gypsum Company Cementitious slurry mixing and dispensing system with pulser assembly and method for using same
GB201508114D0 (en) 2015-05-12 2015-06-24 3M Innovative Properties Co Respirator tab
EP3604248B1 (de) * 2017-03-29 2023-05-03 Sekisui Chemical Co., Ltd. Leuchtendes gekrümmtes glas und gekrümmte digitale beschilderung
JP7231567B2 (ja) * 2017-06-09 2023-03-01 シグニファイ ホールディング ビー ヴィ 光効果を発生させるための光学部品
EP3651887A4 (de) 2017-07-14 2021-04-14 3M Innovative Properties Company Adapter zum fördern mehrerer flüssigkeitsströme
US11396121B2 (en) * 2018-08-20 2022-07-26 N.E.W. Plastics Corp. Extruded variegated plastic profile and method
US11485062B2 (en) 2018-12-19 2022-11-01 The Goodyear Tire & Rubber Company Apparatus for forming an encapsulated strip
CN110406075A (zh) * 2019-07-19 2019-11-05 泉州丰泽春信机械设计有限公司 一种基于异型材海洋板用的梯度式顶压的板材挤出模具
WO2023203390A1 (en) 2022-04-19 2023-10-26 3M Innovative Properties Company Broadband reflectors including polymeric layers, and composite cooling systems
WO2023223114A1 (en) 2022-05-19 2023-11-23 3M Innovative Properties Company Light shielding articles and electromagnetic receivers and/or emitters including the same

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3461197A (en) * 1963-03-22 1969-08-12 Jerome H Lemelson Method for producing composite articles
US3458248A (en) * 1966-10-03 1969-07-29 James F Eversole Light polarizing structure and process therefor utilizing cylindrical-shaped cavities within an isotropic sheet
US3746607A (en) * 1966-11-17 1973-07-17 Johnson & Johnson Sheet material
US4125581A (en) * 1966-12-30 1978-11-14 Rasmussen O B Multi-layer products
US3556635A (en) * 1967-05-23 1971-01-19 Dow Chemical Co Fiber optic bundle
US3616100A (en) * 1967-12-29 1971-10-26 Yoshio Morita Multicolor iridescent plastic product containing crescent shaped nacreous pigment layers
FR2005769A1 (fr) * 1968-04-08 1969-12-19 Rasmussen O B Procede et dispositif pour la fabrication de feuilles en materiau synthetique
US3759647A (en) * 1969-04-10 1973-09-18 Turner Alfrey Us Apparatus for the preparation of multilayer plastic articles
US3565985A (en) * 1969-04-10 1971-02-23 Dow Chemical Co Method of preparing multilayer plastic articles
US3954933A (en) * 1970-07-21 1976-05-04 Societe F. Beghin Reticular structure derived from film and method of manufacturing said structure
US3711176A (en) * 1971-01-14 1973-01-16 Dow Chemical Co Highly reflective thermoplastic bodies for infrared, visible or ultraviolet light
BE789478A (fr) * 1971-10-01 1973-03-29 Dow Chemical Co Procede et dispositif d'extrusion de matieres plastiques en feuilles multicouches
US3884606A (en) * 1971-10-01 1975-05-20 Dow Chemical Co Apparatus for multilayer coextrusion of sheet or film
JPS5310623A (en) * 1976-07-19 1978-01-31 Genjirou Nishibori Side plate moving device of moulding box for production of segments and other concrete products
US4094947A (en) * 1976-09-03 1978-06-13 The Dow Chemical Company Multilayer coextrusion process for producing selective reflectivity
JPS5436387A (en) * 1977-08-25 1979-03-17 Asahi Chem Ind Co Ltd Synthetic resin molded article having multiple layer structure, and method and apparatus for munufacturing the same
US4431711A (en) * 1980-03-25 1984-02-14 Ex-Cell-O Corporation Vacuum metallizing a dielectric substrate with indium and products thereof
US4407871A (en) * 1980-03-25 1983-10-04 Ex-Cell-O Corporation Vacuum metallized dielectric substrates and method of making same
US4440709A (en) * 1980-03-27 1984-04-03 Rasmussen O B Method of manufacturing reticular sheet
GB8305312D0 (en) * 1983-02-25 1983-03-30 Raychem Ltd Curable sheet
US4540623A (en) * 1983-10-14 1985-09-10 The Dow Chemical Company Coextruded multi-layered articles
US4713143A (en) * 1987-04-16 1987-12-15 Davidson Textron Inc. Etching of vacuum metallized indium
US4828780A (en) * 1987-12-01 1989-05-09 Killon Extruders, Inc. Method for encapsulating extruding materials
DE68916311T2 (de) * 1988-04-12 1994-12-15 Jsp Corp Verfahren zur Herstellung einer thermoplastischen Kunststoffolie und deren Verwendung als Puffermaterial.
JPH01301225A (ja) * 1988-05-31 1989-12-05 Seisan Nipponsha Kk リブ付合成樹脂フィルムの製造方法
US5122905A (en) * 1989-06-20 1992-06-16 The Dow Chemical Company Relective polymeric body
US5045264A (en) * 1990-03-29 1991-09-03 Dowbrands, Inc. Method and apparatus for making extruded plastic film with strips embedded therein of a second thermoplastic material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7887660B2 (en) 2004-10-22 2011-02-15 Dow Global Technologies Inc. Composite pipes and method making same
US8043696B2 (en) 2004-10-22 2011-10-25 Dow Global Technologies Llc Microlayer structures and methods
US8685514B2 (en) 2004-10-22 2014-04-01 Dow Global Technologies Llc Composite pipes and method making same
US9227346B2 (en) 2004-10-22 2016-01-05 Dow Global Technologies Llc Plastic composite articles and methods of making same

Also Published As

Publication number Publication date
US5217794A (en) 1993-06-08
EP0647183A1 (de) 1995-04-12
CA2100061A1 (en) 1992-07-23
JP2993736B2 (ja) 1999-12-27
EP0647183A4 (de) 1993-11-08
DE69130118D1 (de) 1998-10-08
US5316703A (en) 1994-05-31
WO1992012857A1 (en) 1992-08-06
ATE170455T1 (de) 1998-09-15
AU1151392A (en) 1992-08-27
FI933294A0 (fi) 1993-07-21
NO932637D0 (no) 1993-07-21
KR930703147A (ko) 1993-11-29
JPH06506408A (ja) 1994-07-21
CN1063449A (zh) 1992-08-12
DE69130118T2 (de) 1999-05-20
FI933294A (fi) 1993-07-21
MX9200263A (es) 1992-07-01

Similar Documents

Publication Publication Date Title
EP0647183B1 (de) Lamellenartig polymerer körper und verfahren zu seiner herstellung
EP0666993B1 (de) Formbarer reflektierender multischichtenkörper
US5122905A (en) Relective polymeric body
EP0663867B1 (de) Vorrichtung zur herstellung von koextrudierten mehrschichtartikeln mit einer grenzschutzschicht
US5234729A (en) Multilayer polymeric reflective bodies for decorative and security applications
EP0514223B1 (de) Optisch verschiedene Zusammensetzungen für reflektierende Kunststoffelemente
US5233465A (en) Visibly transparent infrared reflecting film with color masking
US5262894A (en) Multicomponent, multilayer polymeric reflective bodies
US4162343A (en) Multilayer light-reflecting film
KR100336546B1 (ko) 완전중합체성냉경
EP0491551B1 (de) Reflektierende, mehrschichtige Kunststoffelemente

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930730

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE DK FR GB IT LU MC NL SE

17Q First examination report despatched

Effective date: 19970127

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: THE DOW CHEMICAL COMPANY

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE DK FR GB IT LU MC NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980902

REF Corresponds to:

Ref document number: 170455

Country of ref document: AT

Date of ref document: 19980915

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69130118

Country of ref document: DE

Date of ref document: 19981008

ET Fr: translation filed
ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981202

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981202

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19981202

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19981217

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981218

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981231

NLS Nl: assignments of ep-patents

Owner name: MINNESOTA MINING AND MANUFACTURING COMPANY

BERE Be: lapsed

Owner name: THE DOW CHEMICAL CY

Effective date: 19981231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19981218

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000831

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20000701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051218

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080131

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090701